Ethyl Acetate → 5-Bromo-2-((tert-butyldimethylsilyl)ethynyl)pyridine

HRID 734777ノート

反応式

HRID 734777 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][N:3]=1.[C:9]([Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14])([CH3:12])([CH3:11])[CH3:10].CCOC(C)=O>C1COCC1.C(N(CC)CC)C.[Cu]I>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([C:17]#[C:16][Si:13]([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:15])[CH3:14])=[N:3][CH:4]=1

参加物

7

反応物 3

HCID 8857Ethyl AcetateHCID 693532,5-DibromopyridineHCID 2757281(tert-Butyldimethylsilyl)acetylene

生成物 1

HCID 666112135-Bromo-2-((tert-butyldimethylsilyl)ethynyl)pyridine

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8028Tetrahydrofuran溶媒HCID 8471Triethylamine溶媒

反応条件

温度
0 °C

実験手順

Under an argon atmosphere 0.80 g (4.20 mmol) of CuI and 2.90 g (4.13 mmol) of bis(triphenylphosphane)palladium (II) chloride were added to a solution of 49.90 g (201.0 mmol) of 2,5-dibromopyridine and 43.0 mL (225.6 mmol) of tert-butylethynyldimethylsilane in 500 mL of dry THF and 120 mL of triethylamine at −7° C. and the mixture was stirred for 30 minutes at 0° C. The reaction mixture was stirred for a further 3.5 hours at RT, then filtered and the filtrate was evaporated down in vacuo. The residue was dissolved in 1 L of EtOAc, the organic phase was washed with water and saturated NaCl solution, dried over sodium sulfate, and evaporated down in vacuo. The crude product was reacted further without purification. Yield: 59.5 g (quant. yield); C13H18BrNSi (M=296.278); calc.: molpeak (M+H)+: 296/298 (Br); found: molpeak (M+H)+: 296/298 (Br); Rf value: 0.75 (silica gel, cyc/EtOAc 8:1).

後処理

  1. stirringThe reaction mixture was stirred for a further 3.5 hours at RT
  2. filtrationfiltered
  3. customthe filtrate was evaporated down in vacuo
  4. dissolutionThe residue was dissolved in 1 L of EtOAc
  5. washthe organic phase was washed with water and saturated NaCl solution
  6. dry with materialdried over sodium sulfate
  7. customevaporated down in vacuo
  8. customThe crude product was reacted further without purification

出典と根拠

ORDレコード
ord-5ddbae0132af472593118cea696e65f6
出典データセット
uspto-grants-2009_09
特許番号
US07592358B2

反応ノート

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